Metal-organic frameworks (MOFs) are highly tunable porous crystalline coordination polymers with far-reaching applications. The functionality of these materials can be augmented via post-synthetic modification (PSM) reactions, affording frameworks with rationally designed pore environments. This work involves the development of a novel MOF PSM strategy that harnesses the orthogonality of disulfide bond formation to selectively install an array of structurally and electronically diverse functional groups. The process consists of activation of a thiolated molecule of interest, followed by a subsequent thiol-disulfide exchange reaction with a thiolated MOF. The mild conditions, convenient spectrophotometric monitoring, and high conversions support the addition of this technique to the MOF chemist’s toolkit.

Disulfide-driven pore functionalization of metal-organic frameworks

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